Process for the manufacture of complex metal compounds of polyazo dyestuffs



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Patented Nov. 21, 1939 UNITED STATES PATENT OFF-ICE PROCESS FOR.YTHE-MANUFACTURE OF COM- PLEX METAL COMPOUNDS OF POLYAZO DYESTUFFS Fritz Straub, Basel, and Walter Hanhart, Riehen, Switzerland, assignors to*the: firm; Society of Chemical Industry inBasleg; Basel, Switzerland No Drawing. Application June 15, 1937; Serial- No. 148,410. In Switzerland June 17, 1936 7 Claims; (01. 260--143) It has been found that complexmetal compounds of, polyazo-dyestufis can be. produced if on the one hand, agents yielding metal and on the other hand alkaline reducing agents are caused to react in-the sameworking operation with azo-dyestufis containing atleast one nitrogroup as well as lake-rforming, groups, this reaction being carried out in such-a manner that in addition. to the metallizatio-n .of the dyestufi the nitro-group is converted into such a. reduc-'- tion stage which links two radicals of the amdyestufi by the grouping N=N- or' r the followinggeneral formula R N=N' R NQz two nitro-groups of two dyestufi molecules being reduced until formation'of anazo-bridge or an azoxy-bridge takes place, and the complex metal compound being formed in rthel same operation,

ifnecessary with saponification of the alkoxy 40 groups.

Azo-dyestuffs serving as parent materials for this invention, which maybe mono-, disor polyazoedyestuffs and contain at least onenitro-groupaswell asalake-forminggroup, for instance a substituted or non-substituted hydroxyl group in ortho-position to an azo-bridge, may be made,- for. example, by couplinga diazotized ortho aminophenol containing as a-substituent a nitrogr0up,preferably in para-position to the aminogroup, with any coupling component, for instance amines or phenols, for example hydroxynaphthalenes and especially 1-hydroxynaphthalenes as well as their sulfonic acids, or substances whose coupling carbon-atom belongs to an open chain or a'heterocyclic, ring. Especially suitable The azo-dyestufis serving as parent materials for this invention, which may be illustrated by coupling components are the amino-hydroxynaphthalene sulfonio acids.

The application of the agent which yields metal,

for example chromium, copper or nickel, and the agent which has an alkaline reducing action, for example glucose, in one and the same operation may consist in heating a solution of the dyestuff' in an aqueous caustic alkali, for instance caustic soda solution or caustic potash solution, with the agent that yields metal and the reducing. agent. For example, the agent yielding metal may be added to the dyestuff solution simultaneously with the'reducingagent, or before or afterwards.

The solution is heated inmost cases advantageously to moderately raised temperatures only, for example to 50-60 C. The operation, however, can be carried out in'many cases also at higher or lower temperatures. As reducing agents therev may be used, besidesglucose, also othericarbohydrates which have a reducing action.

Itis advantageous that theactionoi theagent yielding metal should occur in the presence of an organic compound containing hydroxyl groupsv which can form with the metal-yielding agent,

especially an agent yielding copper, compounds stable to dilute-alkali, Such compounds containing hydroxyl groups-are, for example, aliphatic *hydroxyoarb'oxylic acids: (for instance tartaric acid, lactic acid, glycollic acid, tartronic acid, malic acid, dihydroxytartaric acid and saccharic acid), oralcohols (forexample glycerol or glycol) or derivatives of ammonia containing hydroxyl groupsffor example methanolamine and ethanolamine).

The dyestuffs obtainable by the invention may be used for dyeing'iand printing various materials; they are" especially suitable for dyeing vegetable fibers',=.for instance cotton, to which they, impart various tints of very good fastness.

The following examples illustrate the invention,the parts being by weight:

- Example 1 1.7 parts of 5-nitro-2-amino-l-hydroxyben zene are diazotized and coupled with 3.7 parts of 2 .-amino- 5-.-hydroxynaphthalene- 1 :7 -disulfonio acid; the dyestufi thus obtained is separated in the usual manner, filtered, washed'with saltisolu- I tion and dissolved by'addition of 26.5 partsof caustic soda solution of percent. strengthand 300 parts of;water at 60. C. There is thenadded a neutral or feeblyalkaline solution of.2.5 parts.

of crystallized copper sulfate and 3 parts ottartaric acid in v parts o-f:waten'simultaneously,

trated sulfuric acid to a reddish blue solution an about 1 hour at 55-60 C. The dyestufi of the formula HgN- SOgH may be precipitated by addition of acetic acid and common salt. When dry it is a dark powder soluble in water to a blue solution, in concen- HOzS SOaH dyeing cotton in a bath containing Glaubers salt blue tints fast to light.

Example 2 The dyestufi obtained by coupling the diazocompoundfrom 2.2 parts of 4-chloro-5-nitro-2- aminol-hydroxybenzene with 4.1 parts of 1:8- dihydroXynaphthalene-Zl:B-disulfonic acid is separated and dissolved in 200 parts of water and 10.5 parts of caustic soda solution of 30 per cent. strength; this solution is mixed at 60 C. with a neutral or feebly alkaline solution of 2.5 parts of crystallized copper sulfate and 3 parts of tartaric acid in 50 parts of water and simultaneously with a solution of 2 parts of grape sugar in 20 parts of water. C. the'whole is acidified with acetic acid and the dyestufijsalted out. The dyestufi of the formula OH OH when dry is a dark powder soluble in concentrated sulfuric acid to a blue solution and in water to Hogs After stirring for 1 hour at 60 of 10 per cent. strength and at the same time with a solution made from 2.5 parts of crystallized copper sulfate, 3 parts of tartaric acid, 50 parts of water and the quantity of caustic soda solution necessary for neutralization. The whole is stirred for about an hour at 55-60 C. and the dyestufi of the formula N=N N=N or On OH -N N- OH HOaS S0311 precipitated by acidifying with acetic acid and salting out. When dry the dyestuif is a dark powder soluble in concentrated sulfuric acid to a blue-Violet solution and in water to a greenish blue solution; it dyes cotton in a bath containing Glaubers salt green-blue tints fast to light.

Example 4 The dyestuff obtained by coupling the diazo- OH OH been added, and the whole is heated whilst stirring for 1 hour at about 60 C. The dyestufi of a violet solution and dyeing cotton in a bath conthe formula SOaH H0=s NEG N=N N=N N=N our 11 )11 --N N- H H taining Glaubers salt reddish blue tints fast to light.

' Example: 3

1.9 parts of 5-nitro-2-amino-l-hydroxybenzone are diazotized and coupled in the usual manner with 42 parts of l-amino-S-hydroxynaph- 70" thalene-3z6-disulfonic acid in alkaline solution. Theseparated dyestufi is washed with common salt solution and dissolved in 400 parts of water at 60 C. with addition of 33 parts of caustic soda solution of 30 per cent. strength and the solution *is' mixed withZO parts of a solution of grape sugar More or less differing dyestuffs are obtained in accordance with the conditions under which the reduction and coppering are effected; thus a blue dyeing dyestuff is obtained if the metal-yielding agent and the reducing agent are added at difierent periods of time, for example if first the liquor is stirred for a short time with a copper solution at 60 C. and then is reduced;

Example: 5v

The dyestuif obtained" by coupling the diazo- I compound from 1.54 parts of"5-nitro-.2-.amino-1- hydroxybenzene and 4.8 parts of 5:5-dihydroxynow added dissolved in -18 parts of water and simultaneously a solution. of 2.5 parts of, crystallized copper sulfate and 3 parts of tartaric acid in 50 parts of water neutralized or adjusted to slight alkalinity with caustic soda solution. The whole is stirred for 1 hour at about 60 C.'and the dyestufi of the formula HOaS NH -SOaH I aminocarboxylic acid, for instance aminoacetic acid.

Example 6 The dyestufi obtained by coupling the diazocompound from 1.7 parts of 5-nitro-2-amino-1- hydroxybenzene with 4 parts of 2-benzoylamino- 5-hydroxynaphthalene-7sulfonic acid and salting out is dissolvedin 400 parts'of water at 60 C. and the solution is mixed with 33 parts of caustic soda solution of 30 per cent.- strength. There is then added a neutralized solution of 25 parts of crystallized copper sulfate and 3 parts of tartaric acid in 50 parts of water towhich have been added 1.5 parts of grape sugar in the form of a solution of 10 per cent. strength; the whole is now kept for 30 minutes at 55-60? C. After neutralization with dilute acetic acid or mineral acid common salt is added and the cupriferous dyestuff of the formula- HOaS is filtered. The dry dyestuff is, a dark powder.

soluble, in dilute sodium carbonate solution to a blue-violet solution and in concentrated sulfuric acid to a dirty violet solution; it dyes cot ton in a bath containing Glaubers salt bluegreen tints very fast to light.

Example 7 2.4, parts .of. 5..-.nitro=2-amind-l-hydroxyb.enzenej HzN. N=N

s o in are diazotized and coupled in the usual manner in alkaline solution with 3.9 parts of 2-amino-8- hydroxynaphtha1ene-6-sulfonic acid. The dyestuff thus obtained is purified and dissolved in parts of water with addition of 13 parts of caustic soda solution of 30 per cent. strength and a neutral solution of 2.5 parts of crystallized copper sulfate and 3 parts of tartaric acid in 50 parts of water together with'a solution of -10 per cent. strength of grape sugar containing. 1.5 parts of the latter. After stirring for'l hour. at 55-60 C. the whole is neutralized approximately with'dilute acid, common salt is added ifv necessary and the dyestuff of the formula 0!. OH N N,-

filtered. When ,dry it is a dark powder. soluble in concentrated sulfuric acid and dilute caustic soda solution to blue solutions and dyeing cotton 5 2 1 in a bath containing Glaubers saltblue-grey tints very fast to light.

Example 8 2.6 parts of 5-nitro-2-amino-l-hydroxybenzene are diazotized and coupled with 4.2 parts of 1- alkaline solution.

caustic soda solution of 30 per cent. strength in 300 parts 'of Water at 60 C., at which tempera ture there is added a neutral or alkaline S0111? tion of 2.5 parts of crystallized copper sulfate and 3 parts of tartaric acid in 50 parts of water to which 1.5 parts of grape sugar in the form of a solution of 10 per cent. strength has been added: and the whole is, heated whilst stirring forl hour at about 60 C. Some common salt is now added. and the mixture is neutralized with dilute mineral. acid until brilliant paper shows only a feeble Q alkaline reaction, whereupon the dyestufi of the is precipitated. When dry the dyestufi" is a dark powder soluble in concentrated; sulfuric acid and in water to blue solutions and dyeing cotton and viscose in a bath containing Glaubers salt greenish grey tints very fast to light.

Example 9 1.7. parts of 5-nitro-2-amino-l-hydroxybenzene are-diazotized and coupled. with 4.4e.parts;of: 2

(4"- hydroxy 3- carboxy) -phenylamino 5- hydroxynaphthalene-7-sulfonic acid. The dyestufi thus obtained is separated, purified, dissolved in 250 parts of water at 60 C. with addition of 24 parts of caustic soda solution of 30 per cent.

strength and then treated for about 10 minutes with an agent yielding copper which may consist of a solution of 2.5 parts of crystallized copper sulfate and 3 parts of tartaric acid and 50 parts of water and the quantity of caustic soda solution necessary for neutralization. 1.8 parts of grape sugar forming a solution of 10 per cent. strength H038 S 03H "is now added and the mixture is heated for an hour at 60 C., then acidified with acetic acid and finally the dyestufi of the formula salted out. When dry it is a dark powder soluble in water and in concentrated sulfuric acid to blue solutions and dyeing cotton and artificial silk from regenerated cellulose blue tints in a bath containing Glaubers salt.

Example 10 a the formula @NH no.0

is precipitated in larger part complete precipitation is attained by addition of a dilute acid until the reaction is only feebly alkaline. The dry dyestufi? is a dark powder soluble in concentrated sulfuric acid and iridilute alkali solution to blueviolet solutions and dyeing cotton in a bath containing Glauber's salt grey tints.

Example 11 The dyestufi obtained by coupling the diazocompound .from 3.8.parts of 5-nitro-2-amino-1- hydroxybenzene with. 12.2 parts of 8:8'-dihydroxy-Z 2'-dinaphtl1ylamine-6 6-disulfonic acid is separated, "purified and dissolved in 200 parts of water at 60 C. with the aid of parts of caustic soda solution of per cent. strength. To the solution is added a neutral solution of 2.5 parts of crystallized copper sulfate and 3 parts of tartaric acid in 50 parts of water and at the same time 1.8 parts of grape sugar in the form of a solution of 10 per cent. strength. The whole is.

heated while stirring for about 1 hour at 55-60 C. and the dyestuff of the formula on on I On N 011 1105s sonar is precipitated by means of common salt and dilute acid added until the alkaline reaction is feeble. The dry dyestufi is a. dark powder soluble in concentrated sulfuric acid to a violet solution and in water to a reddish blue solution. It dyes cotton in. a bath containing Glaubers salt greenish grey fast tints.

Example 12 I 5.8 parts of the sodium salt of the dyestufi from diazotized 2-amino-5-nitro 1 methoxy-benzene and 2 -(3'- carboxy phenylamino) 8 hydroxynaphthalene-G-sulfonic acid are dissolved in the form of a paste in 500 parts of water at 65 C. with the aid of 6.2 parts of caustic soda solution of 30 per cent. strength; after addition of 1.3 parts of glucose in the form of a solution of 10 per cent. strength the solution is heated for about hour at 65-'70 C It is then neutralized with dilute acid until brilliant yellow paper shows only weak alkalinity. After addition of the solution obtained from 3 partsof crystallized copper sul- N=N NH OH H038 H0O C is filtered and dried. It is a dark powder soluble in water to a dull violet solution and in concentratedsulfuric acid to a greenish blue solution.

It dyes cotton in a bath containing Glaubers salt fast-grey tints.

' Example 13 5.3 parts of the sodium salt of the azo-dyestuif from v diazotized 2-amino-5-nitro 1 methoxybenzene and l-hydroxynaphthalene-3:G-disulfonic acid are dissolved in 300 parts of water with the aid of 9.3 parts of caustic soda solution of 30 per cent. strength. At a temperature of about 75 C. and in the course of /2 hour 1.2 parts of grape sugar dissolved in 12 parts of water are added by drops and then the whole is stirred for a further /z hour at the same temperature. After the mass has been neutralized with acetic acid and has been mixed with a solution made from 3 parts of crystallized copper sulfate, 12 parts of water and 9 parts of a solution of ammoniaof per cent. strength 10 hours at 80-90 C. After neutralization with acetic acid the dyestuff of the formula the whole is'heated for about the azo-group, this reaction being carried out I in such a manner that in addition to the metalis salted out. When dry it is a dark powder soluble in water to a reddish blue solution and in concentrated sulfuric acid to a greenish blue solution, and dyeing cotton in a bath containing Glaubers salt blue tints.

Example 14 5.3 parts of the azo-dyestuff from diazotized 2-amino-5-nitro-l-methoxybenzene and 2-hy-v droxynaphthalene-5:7-disulfonic acid are dissolved in-300 parts of water with addition of 7.8

about 12 hours at 80-90 C. After acidifying lization of the dyestuff the nitro-group is con- .verted into such a reduction stage which links two radicals of the azo-dyestuff by a member of the group consisting of -N=N- and o 3. Process for the manufacture of complex metal compounds of polyazo-dyestufis, which comprises causing agents yielding metal and alkaline reducing agents to react in the same working operation with azo-dyestuffs of the general formula RrN=N-Rz-N 0 2 wherein R1 represents a naphthaleneradical which is linked in 2-position with the azo-group and R2 represents a benzene radical, wherein further the hydroxyl groups of the radicals R1 and R2 stand in ortho-position to the azo-group and the nitro-group stands in para-position to with acetic acid the dyestuff of the formula the azo-group, this reacion being carried out in --N=N N=N N=N H0|S OH or E0 30311 H --N OH on reddish blue tints in a bath containing Glaubers salt.

What we claim is:

1. Process for the manufacture of complex metal compounds of polyazo-dyestuffs, which comprises causing agents yielding metal and alkaline reducing agents to react in the same working operation with azo-dyestuffs containing at least one nitro-group in para-position to an azo-group as well as lake-forming groups, this reaction being carried out in such a manner that in addition to the metallization of the dyestuif the nitro-group is converted into such a reduction stage which linkstwo radicals of the azo-dyestuff radicals of the azo-dyestuff by a member of the group consisting of N=N- and 4. Process for the manufacture of complex copwhich is linked in 2-position with the azo-group and R2 represents a benzene radical, wherein further the hydroxyl groups of the radicals R1 and R2 stand in ortho-position to the azo-group and the nitro-group stands in para-position to wherein R1 represents a naphthalene radical which is linked in Z-position with the azo-group and R2 represents a benzene radical, wherein further the hydroxyl groups of the radicals R1 and R2 stand in ortho-position to the azo-group and the nitro-group stands in para-position to the azo-group, this reaction being carried out in such a manner that in addition to the formation of the copper compound of the dyestuff the nitrogroup is converted into such a reduction stage which links two radicals of the azo-dyestuff by amember of the group consisting of N=N- and 6. Process for the manufacture of complex copper compounds of polyazo-dyestufis, which comprises causing grape sugar and agents yielding copper to react in an alkaline medium and in the presence of organic compounds containing hydroxyl groups in the same working operation with azo-dyestuffs of the general formula wherein R1 represents a naphthalene radical which is linked in Z-position with the azo-group and R2 represents a benzene radical, wherein further the hydroxyl groups of the radicals R1 and R2 stand in ortho-position to the azo-group and the nitro-group stands in para-position to the azo-group, this reaction being carried out in such a manner that in addition to the formation of the copper compound of the dyestuff the nitro-group is converted into such a reduction stage which links two radicals of the azo-dyestufl by a member of the group consisting of --N=N- and 7. Process for the manufacture of complex copper compounds of polyazo-dyestuffs, which comprises causing grape sugar and agents yielding copper to react in an alkaline medium and in the presence of salts of tartaric acid in the same working operation with azo-dyestufis of the general formula wherein R1 represents a naphthalene radical which is linked in 2-position with the azo-group and R2 represents a benzene radical, wherein further the hydroxyl groups of the radicals R1 and R2 stand in ortho-position to the azo-group and the nitro-group stands in para-position to the azo-group, this reaction being carried out in such a manner that in addition to the formation of the copper compound of the dyestuif the nitrogroup is converted into such a reduction stage which links two radicals of the azo-dyestufi by a member of the group consisting of -N=N and FRITZ STRAUB. WALTER HAN'HART. 

